EP0645999B2 - Method for dyeing keratin fibres with indole or indolin derivatives, hydrogen peroxide and a peroxidase - Google Patents

Abstract

A method for dyeing keratin fibres by applying thereto: a component (1) consisting of an aqueous dyeing medium containing a compound of formula (I) or (II), wherein R1 is hydrogen or alkyl; R2 is hydrogen, alkyl or COOH; R3 is hydrogen or alkyl; X is hydrogen, OH, NH2, alkyl or alkoxy; and Y is OH or NH2; a component (2) consisting of an aqueous dyeing medium containing a peroxidase enzyme; and a component (3) containing hydrogen peroxide or an enzymatic hydrogen peroxide source; said component (1) being applied first and separately from component (3).

Description

The invention relates to a process for dyeing keratin fibers using indole or indoline derivatives, hydrogen peroxide and an enzyme-peroxidase.

Hair coloring called "permanent" is to obtain a visible color on the hair for several weeks, resistant to shampoos.

For this purpose, it is possible to use indole or indolinic precursors capable of being oxidized in the presence of an oxidizing agent to give colored products whose chemical structure is similar to hair pigments such as melanin.

The oxidizing agent commonly used is hydrogen peroxide.

The oxidation dye precursors chosen from indole or indolinic derivatives have the advantage of producing colorations close to natural shades.

The prior art oxidation dyeing processes using indole or indolinic precursors and hydrogen peroxide as the oxidant system are generally carried out in alkaline dyeing media to obtain satisfactory dyeing properties. . However, the application of these alkaline media causes degradation in the fibers.

FR-A-2,252,841 describes a hair dyeing process.

The Applicant has surprisingly discovered a new process for the oxidation dyeing of keratinous fibers based on indole or indolinic derivatives which, after oxidation with hydrogen peroxide in the form of hydrogen peroxide or produced by an enzymatic natural source, in presence of a peroxidase enzyme, allowed to obtain, under mild pH conditions, powerful colorings, resistant to shampoos, without degradation of the fibers.

The subject of the invention is therefore a new dyeing process employing at least one indole or indolinic derivative, hydrogen peroxide and an enzyme-peroxidase.

Another object of the invention is constituted by the compositions and devices with several compartments used in the context of this process.

Other objects will appear on reading the description and examples which follow.

• un composant (1) contenant dans un milieu aqueux approprié pour la teinture, au moins un composé de formule :
  
  dans lesquelles :
  • R₁ représente un atome d'hydrogène ou un radical alkyle en C₁-C₄;
  • R₂ représente un atome d'hydrogène, un radical alkyle en C₁-C₄ ou -COOH;
  • R₃ représente un atome d'hydrogène ou un radical alkyle en C₁-C₄ ;
  • X désigne un atome d'hydrogène. NH₂, OH, un radical alkyle en C₁-C₄ ou un radical alcoxy en C₁-C₄;
  • Y désigne OH ou NH₂ ;
  • sous réserve que lorsque X désigne OH ou alkyle, X occupe les positions 5, 6 ou 7 et X est en position ortho par rapport à Y ;
• un composant (2) contenant dans un milieu aqueux approprié pour la teinture, au moins une enzyme-peroxydase ;
• un composant (3) contenant dans un milieu aqueux approprié pour la teinture, au moins du peroxyde d'hydrogène ou une source de peroxyde d'hydrogène enzymatique ;

The process for dyeing keratinous fibers, and in particular hair, according to the invention is characterized in that at least the following are applied to these fibers:

• a component (1) containing in an aqueous medium suitable for dyeing, at least one compound of formula:
  
  in which :
  • R ₁ represents a hydrogen atom or a C ₁ -C ₄ alkyl radical;
  • R ₂ represents a hydrogen atom, a C ₁ -C ₄ alkyl radical or -COOH;
  • R ₃ represents a hydrogen atom or a C ₁ -C ₄ alkyl radical;
  • X denotes a hydrogen atom. NH ₂ , OH, a C ₁ -C ₄ alkyl radical or a C ₁ -C ₄ alkoxy radical;
  • Y is OH or NH ₂ ;
  • provided that when X is OH or alkyl, X is at positions 5, 6 or 7 and X is ortho to Y;
• a component (2) containing in an aqueous medium suitable for dyeing, at least one enzyme-peroxidase;
• a component (3) containing in an aqueous medium suitable for dyeing, at least hydrogen peroxide or a source of enzymatic hydrogen peroxide;

• soit dans une deuxième étape une composition contenant dans un milieu aqueux approprié pour la teinture au moins les composants (2) et (3), la composition contenant le composant (1) ne contenant pas le composant (2),
• soit dans une deuxième étape une composition contenant dans un milieu aqueux approprié pour la teinture le composant (2) et dans une troisième étape une composition contenant dans un milieu aqueux approprié pour la teinture le composant (3), la composition contenant le composant (1) ne contenant pas le composant (2)
• soit dans une deuxième étape une composition contenant dans un milieu aqueux approprié pour la teinture le composant (3) lorsque la composition appliquée dans la première étape contient le composant (2),

le pH des compositions mises en oeuvre variant de 4,5 à 7,5.the component (1) being applied to the fibers first, separately from the component (3),
in which one applies
in a first step, a composition containing, in an aqueous medium suitable for dyeing, at least component (1) and optionally component (2), and then

• in a second step, a composition containing in an aqueous medium suitable for dyeing at least the components (2) and (3), the composition containing the component (1) not containing the component (2),
• in a second step, a composition containing in an aqueous medium suitable for dyeing the component (2) and in a third step a composition containing in an aqueous medium suitable for dyeing the component (3), the composition containing the component (1) ) not containing component (2)
• in a second step, a composition containing in an aqueous medium suitable for dyeing the component (3) when the composition applied in the first step contains the component (2),

the pH of the compositions used ranging from 4.5 to 7.5.

Among the preferred indole or indoline precursors of formula (I) or (II), there may be mentioned 5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 3-methyl-5,6-dihydroxyindole, 4- hydroxyindole, 2,3-dimethyl-5,6-dihydroxyindole, 6-hydroxy-5-methoxyindole, 6-hydroxyindole, 5-hydroxyindole, 7-hydroxyindole, 7-aminoindole, 5-aminoindole, acid 5,6-dihydroxyindole 2-carboxylic acid, 4-aminoindole, 1-methyl-5,6-dihydroxyindole, 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline; N-ethyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 4-hydroxy-5-methoxyindoline, 6-hydroxy-7-methoxyindoline, 6,7-dihydroxyindoline, 4,5-dihydroxyindoline, 5-methoxy-6-hydroxyindoline and their salts.

The enzyme-peroxidase used in accordance with the invention is an enzyme encoded 1.11.1. according to the enzyme classification system (Enzyme Nomenclature, 1984, Academic Press Inc.).

By way of example, peroxidases from natural sources such as horseradish, turnip, fig, cow's milk or soya can be mentioned. They are used according to the invention at different degrees of purification and at varying amounts depending on the degree of purity.

In particular, horseradish peroxidases such as the products sold by SIGMA are used.

The peroxidases according to the present invention are used in amounts of between 100 and 40,000 catalytic units of peroxidase per 100 g of components (1), (2) and (3) as defined above, to be applied to the hair; the catalytic units being determined during the pyrogallol oxidation reaction with hydrogen peroxide at pH 6 and 20 ° C. (a catalytic unit makes it possible to transform 1 mg of pyrogallol into purpurogallin in 20 seconds).

In the case where oxidizing agent is used as hydrogen peroxide solution, the amounts of peroxidase are preferably between 1000 and 20,000 catalytic units.

The sources of enzymatic hydrogen peroxide according to the present invention consist of one or more natural substrate (s) associated with one or more enzymatic system (s) of the oxidase type catalyzing the oxidation of a substrate molecule by an oxygen molecule by transfer of a single oxygen atom.

Among the natural substrates used, mention may be made of glucose, uric acid, alcohols, amino acids and lactic acid. They are used at concentrations of preferably between 1 and 25% by weight and more particularly between 3 and 15% by weight relative to the total weight of component (s) (2) and / or (3).

The enzymatic systems of the oxidase type according to the invention are chosen from the oxidases coded 1.x.3, catalyzing the oxidation of a substrate molecule by an oxygen molecule by transfer of a single atom of the molecule of oxygen. The quantities used are determined according to their purity. They preferably vary between 100 and 20,000 catalytic units of oxidase per 100 g of components (1), (2) and (3) to be applied to the keratinous fibers; the units being determined in the air oxidation reaction of the substrate at pH 5.1 and 37 ° C. (an oxidase unit makes it possible to transform 1 μg of substrate in 1 minute).

• glucose/glucose oxydase
• galactose/galactose oxydase
• pyranose/pyranose oxydase
• L-sorbose/L-sorbose oxydase
• éthanol/alcool oxydase (1.1.3.13)
• isopropanol/alcool secondaire oxydase (1.1.3.18)
• acide pyruvique/pyruvate oxydase
• acide oxalique/oxalate oxydase
• acide aspartique/aspartate oxydase
• acide glutamique/L-glutamate oxydase
• acide urique/uricase
• acide lactique/lactate oxydase,

ou leurs mélanges.Among the natural substrate / oxidase substrate oxygen substrate systems by transfer of a single oxygen atom, there may be mentioned:

• glucose / glucose oxidase
• galactose / galactose oxidase
• pyranose / pyranose oxidase
• L-sorbose / L-sorbose oxidase
• ethanol / alcohol oxidase (1.1.3.13)
• isopropanol / alcohol secondary oxidase (1.1.3.18)
• pyruvic acid / pyruvate oxidase
• oxalic acid / oxalate oxidase
• aspartic acid / aspartate oxidase
• glutamic acid / L-glutamate oxidase
• uric acid / uricase
• lactic acid / lactate oxidase,

or their mixtures.

An embodiment of the invention consists in applying to the keratinous fibers, initially, a composition (A) containing in an aqueous medium suitable for dyeing, the component (1) as defined above, and in a second step, a composition (B) containing in an aqueous medium suitable for dyeing, at least the components (2) and (3) as defined above.

Rinsing can be done between the two applications.

The exposure time of the first composition (A) preferably varies between 20 seconds and 20 minutes when the component (3) contains an aqueous solution of hydrogen peroxide or from 1 minute to 1 hour when the component (3) contains a source of enzymatic hydrogen peroxide and that of the second composition (B) between 1 minute and 1 hour and more particularly between 5 minutes and 20 minutes.

A second embodiment of the invention consists in successively applying to the fibers a first composition (C) containing the components (1) and (2), then a second composition (D) containing in a medium suitable for dyeing, the component (3). The exposure time of the composition (C) preferably varies between 20 seconds and 20 minutes, that of the composition (D) between 1 minute and 1 hour and more particularly between 5 and 20 minutes.

A third embodiment of the invention consists in successively applying to the fibers, a composition (E) containing the component (1), a composition (F) containing the component (2) and a composition (G) containing the component ( 3).

The exposure times of the compositions (E) and (F) preferably vary between 20 seconds and 20 minutes, that of the composition (G) preferably varies between 1 minute and 1 hour and more particularly between 5 and 20 minutes.

Depending on the different forms of dyeing processes of the invention, final rinsing and drying may be performed at the end of the treatment.

The alkalinizing agents that may be used in these compositions may in particular be amines such as alkanolamines, alkylamines, hydroxides or alkali or ammonium carbonates.

The acidifying agents that may be used in the compositions of the invention may be chosen from lactic acid, acetic acid and tartaric acid; phosphoric acid, hydrochloric acid and citric acid.

The dyeing compositions (A), (C) and (E) as defined above, contain the indole or indoline derivatives of formula (I) or (II) in concentrations of preferably between 0.2 and 5% by weight per relative to the total weight of each of these compositions.

They may additionally contain a cosolvent chosen from lower alcohols such as ethyl alcohol or isopropanol; glycol ethers such as monomethyl, monoethyl or monobutyl ethers of ethylene glycol or diethylene glycol, monomethyl ethers of propylene glycol and dipropylene glycol; glycol esters such as monomethyl ether acetate or ethylene glycol monoethyl ether acetate; glycols such as ethylene glycol, propylene glycol; lower esters such as methyl lactate.

The preferred solvents are ethyl alcohol and propylene glycol.

The solvents are present in concentrations of preferably between 0.5 and 75% and in particular between 2 and 50% by weight relative to the total weight of the composition.

The dyeing compositions according to the invention may contain other dyes usually used for dyeing keratinous fibers, especially direct dyes such as nitrobenzene derivatives, azo dyes, anthraquinones, naphthoquinones and benzoquinones or oxidation dyes. para or ortho type and / or couplers.

The oxidizing compositions of the invention, such as compositions (B), (D) or (G) as defined above, contain hydrogen peroxide in amounts of between 0.03 and 10% and preferably between 0.05 and 5% by weight relative to the total weight of one of these compositions.

The compositions used in the various dyeing processes of the invention may furthermore contain various adjuvants such as anionic, cationic, nonionic or amphoteric surfactants or mixtures thereof, thickening agents, perfumes, agents and the like. sequestering agents, agents for treating keratinous fibers, dispersing agents, conditioning agents, agents for swelling keratinous fibers, preserving agents.

The compositions used in the various dyeing processes of the invention may be in the form of more or less thickened lotions, gels or emulsions. '

In order to implement the various forms of dyeing process according to the invention, the compositions may be packaged in multi-compartment devices, also called "kits" or "dyeing kits", comprising all the components (1), (2) and (3) intended to be applied for the same dyeing on keratinous fibers.

According to one embodiment, the kit or dyeing kit comprises a first compartment containing a composition (A) as defined above and a second compartment containing a composition (B) as defined above.

Another embodiment consists of a dyeing kit comprising in a first compartment, a composition (C) and in a second compartment, a composition (D) as defined above.

Another embodiment consists of a dyeing kit comprising three compartments, one of which is a composition (E), the second a composition (F) and the third a composition (G).

The following examples are intended to illustrate the invention without being limiting in nature.

EXAMPLES OF COMPOSITIONS EXAMPLE 1 Composition (A1)

- 5.6-Dihydroxyindole 1 g - Ethyl alcohol 10 g - Demineralized Water qsp 100 g The pH of the solution is 6.4.

Composition (B1)

- horseradish peroxidase 2600 units - 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 2.5 g - Monoethanolamine qs pH = 5.1 - Demineralized Water qsp 100 g

The first composition is applied to the hair and left for 15 minutes. We rinse. The second composition is applied by standing for 15 minutes. We rinse. It is noted after shampooing that the hair, initially white, is brown. The acquired hue easily resists several shampoos.

EXAMPLE 2 Composition (A2)

- 5,6-dihydroxyindole 0.5 g - Ethyl alcohol 10 g - Demineralized Water qsp 100 g The pH of the solution is 6.5.

Composition (B2)

- Horseradish peroxidase 1300 units - 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 62 g - Monoethanolamine qs pH = 5.5 - Demineralized Water qsp 100 g

The same process as for Example 1 is used. It is noted after shampooing that the hair, initially white, is light brown in color.

EXAMPLE 3 Composition (C3)

- 5,6-dihydroxyindole 1.5 g - Horseradish peroxidase 3000 units - Ethyl alcohol 10 g - Demineralized Water qsp 100 g The pH of the solution is 6.5.

Composition (D3)

- 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 12 g - Monoethanolamine qs pH = 6 - Demineralized Water qsp 100 g

The first composition is applied to the hair and left for 5 minutes. Without rinsing, the second composition is applied leaving for 20 minutes. It is noted after shampooing that the hair, initially white, is brown.

EXAMPLE 4 Composition (E4)

- 5,6-dihydroxyindole 1 g - Ethyl alcohol 10 g - Demineralized Water qsp 100 g The pH of the solution is 6.5.

Composition (F4)

- Horseradish peroxidase 3000 units - Demineralized Water qsp 100 g

Composition (G4)

- 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 2.5 g - Monoethanolamine qs pH = 6 - Demineralized Water qsp 100 g

The first composition is applied to the hair and left for 5 minutes. We rinse the hair. The second composition is applied to the hair and left for 5 minutes. The third composition is applied leaving for 15 minutes. We rinse. It is noted after shampooing that the hair, initially white, is brown.

EXAMPLE 5 Composition (A5)

- 2-methyl-5,6-dihydroxyindole hydrobromide 1 g - Ethyl alcohol 10 g - Triethanolamine qs pH = 7 - Demineralized Water qsp 100 g

Composition (B5)

- Horseradish peroxidase 2600 units - 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 2.5 g - Triethanolamine qs pH = 5.5 - Demineralized Water qsp 100 g

The same process as in Example 1 is used. A light brown color is obtained on initially white hair.

EXAMPLE 6 Composition (A6)

- 3-methyl-5,6-dihydroxyindole 1 g - Ethyl alcohol 10 g - Conservative qs - Triethanolamine qs pH = 6.8 - Demineralized Water qsp 100 g

Composition (B6)

- Horseradish peroxidase 2600 units - 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 2.5 g - Monoethanolamine qs pH = 5.5 - Demineralized Water qsp 100 g

The same method as in Example 1 is used. A brown coloration is obtained on initially white hair.

EXAMPLE 7 Composition (A7)

- 4-hydroxyindole 1 g - Ethyl alcohol 10 g - Ammonia at 20% qs pH = 7 - Demineralized Water qsp 100 g

Composition (B7)

- Horseradish peroxidase 1600 units - 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 2.5 g - Monoethanolamine qs pH = 5.5 - Demineralized Water qsp 100 g

The same method as in Example 1 is used. A brown coloration is obtained on initially white hair.

EXAMPLE 8 Composition (A8)

2,3-Dimethyl-5,6-dihydroxyindole hydrobromide 1 g - Ethyl alcohol 10 g - Triethanolamine qs pH = 7 - Demineralized Water qsp 100 g

Composition (B8)

- Horseradish peroxidase 2600 units - 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 2.5 g - Monoethanolamine qs pH = 5.5 - Demineralized Water qsp 100 g

The same method as in Example 1 is used. A light brown coloration is obtained on initially white hair.

EXAMPLE 9 Composition (A9)

- 6-hydroxy-5-methoxyindole 1 g - Ethyl alcohol 10 g - Triethanolamine qs pH = 5.5 - Demineralized Water qsp 100 g

Composition (B9)

- Horseradish peroxidase 2600 units - 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 2.5 g - Monoethanolamine qs pH = 5.5 - Demineralized Water qsp 100 g

The same method as in Example 1 is used. A light brown coloration is obtained on initially white hair.

EXAMPLE 10 Composition (A10)

- 6-hydroxyindole 1 g - Ethyl alcohol 10 g - Triethanolamine qs pH = 7 - Demineralized Water qsp 100 g

Composition (B10)

- Horseradish peroxidase 2600 units - 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 2.5 g - Monoethanolamine qs pH = 5.5 - Demineralized Water qsp 100 g

The same method as in Example 1 is used. A brown coloration is obtained on initially white hair.

EXAMPLE 11 Composition (A11)

- 5-hydroxyindole 1 g - Ethyl alcohol 10 g - Triethanolamine qs pH = 6.8 - Demineralized Water qsp 100 g

Composition (B11)

- Horseradish peroxidase 2600 units - 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 2.5 g - Monoethanolamine qs pH = 5.5 - Demineralized Water qsp 100 g

The same method as in Example 1 is used. A dark blond coloration is obtained on initially white hair.

EXAMPLE 12 Composition (A12)

- 7-hydroxyindole 1 g - Ethyl alcohol 10 g - Triethanolamine qs pH = 7 - Demineralized Water qsp 100 g

Composition (B12)

- Horseradish peroxidase 3600 units - 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 2.5 g - Monoethanolamine qs pH = 5.5 - Demineralized Water qsp 100 g

The same method as in Example 1 is used. An iridescent brown coloration is obtained on initially white hair.

EXAMPLE 13 Composition (A13)

- 7-aminoindole 1 g - Ethyl alcohol 10 g - Triethanolamine qs pH = 5.6 - Demineralized Water qsp 100 g

Composition (B13)

- Horseradish peroxidase 2600 units - 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 2.5 g - Monoethanolamine qs pH = 5.5 - Demineralized Water qsp 100 g

The same method as in Example 1 is used. A light brown coloration is obtained on initially white hair.

EXAMPLE 14 Composition (A14)

- 5,6-Dihydroxyindole 2-carboxylic acid 1 g - Ethyl alcohol 10 g - Triethanolamine qs pH = 7 - Demineralized Water qsp 100 g

Composition (B14)

- Horseradish peroxidase 2600 units - 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 2.5 g - Monoethanolamine qs pH = 5.5 - Demineralized Water qsp 100 g

The same method as in Example 1 is used. A light brown coloration is obtained on initially white hair.

EXAMPLE 15 Composition (A15)

- 5-aminoindole 1 g - Ethyl alcohol 10 g - Demineralized Water qsp 100 g

Composition (B15)

- Horseradish peroxidase 3000 units - 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 2.5 g - Monoethanolamine qs pH = 5.8 - Demineralized Water qsp 100 g

The same method as in Example 1 is used. A brown coloration is obtained on initially white hair.

EXAMPLE 16 Composition (A16)

- 4-aminoindole 0.5 g - Ethyl alcohol 10 g - Triethanolamine qs pH = 6.5 - Demineralized Water qsp 100 g

Composition (B16)

- Horseradish peroxidase 2600 units - 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 2.5 g - Monoethanolamine qs pH = 6 - Demineralized Water qsp 100 g

The same method as in Example 1 is used. A brown coloration is obtained on initially white hair.

EXAMPLE 17 Composition (A17)

- 1-methyl-5,6-dihydroxyindole 1 g - Ethyl alcohol 10 g - Triethanolamine qs pH = 7 - Demineralized Water qsp 100 g

Composition (B17)

- Horseradish peroxidase 2600 units - 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 2.5 g - Monoethanolamine qs pH = 5.9 - Demineralized Water qsp 100 g

The same method as in Example 1 is used. A brown coloration is obtained on initially white hair.

EXAMPLE 18

A fresh horseradish tuber is finely ground using a blender, a commercially available food processor. The ground material is used in the manufacture of the second composition of this example.

Composition (A18)

- 5,6-dihydroxyindole 1 g - Ethyl alcohol 10 g - Demineralized Water qsp 100 g The pH of the solution is 6.4.

Composition (B18)

- Fresh horseradish mash 10 g - 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 2.5 g - Monoethanolamine qs pH = 5.5 - Demineralized Water qsp 100 g

The first composition is applied to the white hair and left for 15 minutes. We rinse. The second composition is applied by standing for 15 minutes. We rinse. It is noted after shampooing that the hair is brown.

EXAMPLE 19 Composition (A19)

- 5,6-dihydroxyindoline 1 g - Ethyl alcohol 10 g - Triethanolamine qs pH = 7 - Demineralized Water qsp 100 g

Composition (B19)

- Horseradish peroxidase 2600 units - 20-volume hydrogen peroxide (acidified to pH 2 by orthophosphoric acid) 2.5 g - Monoethanolamine qs pH = 5.9 - Demineralized Water qsp 100 g

The same method as in Example 1 is used. A brown coloration is obtained on initially white hair.

EXAMPLE 20 Composition (A20)

- 5,6-dihydroxyindole 1.5 g - Triethanolamine qs pH = 6.5 - Ethanol 10 g - Demineralized Water qsp 100 g

Composition (B20)

- Glucose 10 g - Glucose oxidase 15000 units - Horseradish peroxidase 2600 units - Demineralized Water qsp 100 g The pH of this composition is 6.8.

The first composition is applied to a lock of hair, initially white, and left for 15 minutes. We rinse. The second composition is applied and left for 15 minutes. Final rinse and drying complete the operation. The coloration obtained is light brown.

EXAMPLE 21 Composition (A21) Identical to the composition (A20) of Example 20. Composition (B21)

- Mixture (80/20) of cetylstearyl and cetylstearyl alcohols oxyethylenated with 33 moles of ethylene oxide, sold under the name LANOL CTO by the company SEPPIC 2 g - Glycerin 0.4 g - Glucose 10g g - Glucose oxidase 15000 units - Horseradish peroxidase 2600 units - Orthophosphoric acid qs pH = 7 - Demineralized Water qsp 100 g

The first composition is applied to a lock of hair, initially white, and left for 15 minutes. We rinse. The second composition is applied and left for 15 minutes. Final rinse and drying complete the operation. The coloration obtained is brown.

EXAMPLE 22 Composition (A22) Identical to the composition (A20) of Example (20) Composition (B22)

- Lactic acid 5 g - Lactate oxidase 200 units - Horseradish peroxidase 2600 units - Monoethanolamine qs pH = 7.5 - Demineralized Water qsp 100 g

The first composition is applied to hair initially white, and left for 15 minutes. We rinse. The second composition is applied and left for 45 minutes. Final rinse and drying complete the operation. The coloration obtained is dark blond.

Claims (19)

1. Process for dyeing keratinous fibres, characterized in that at least:

   - a component (1) comprising, in an aqueous medium appropriate for dyeing, at least one indole or indoline compound of formula:

   

   in which:

   R₁ represents a hydrogen atom or a C₁-C₄ alkyl radical;

   R₂ represents a hydrogen atom, a C₁-C₄ alkyl radical or -COOH;

   R₃ represents a hydrogen atom or a C₁-C₄ alkyl radical;

   X denotes a hydrogen atom, NH₂, OH, a C₁-C₄ alkyl radical or a C₁-C₄ alkoxy radical;

   Y denotes OH or NH₂;

   with the proviso that, when X denotes OH or alkyl, X occupies the 5, 6 or 7 position and Y is in the ortho position with respect to the X group;

   - a component (2) comprising, in an aqueous medium appropriate for dyeing, at least one peroxidase;

   - a component (3) comprising, in an aqueous medium appropriate for dyeing, at least hydrogen peroxide or one source of enzymatic hydrogen peroxide;
   are applied to these fibres;
   the component (1) being applied to the fibres first, separately from the component (3),
   in which process:
   in a first stage, a composition comprising, in an aqueous medium appropriate for dyeing, at least the component (1) and optionally the component (2) is applied, then

   - either, in a second stage, a composition comprising, in an aqueous medium appropriate for dyeing, at least the components (2) and (3) is applied, the composition comprising the component (1) not comprising the component (2),

   - or, in a second stage, a composition comprising, in an aqueous medium appropriate for dyeing, the component (2) is applied and, in a third stage, a composition comprising, in an aqueous medium appropriate for dyeing, the component (3) is applied, the composition comprising the component (1) not comprising the component (2),

   - or, in a second stage, a composition comprising, in an aqueous medium appropriate for dyeing, the component (3) is applied when the composition applied in the first stage comprises the component (2),

   the pH of the compositions employed varying from 4.5 to 7.5.
2. Process according to Claim 1, characterized in that the component (1) comprises an indole or indoline compound chosen from 5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 3-methyl-5,6-dihydroxyindole, 4-hydroxyindole, 2,3-dimethyl-5,6-dihydroxyindole, 6-hydroxy-5-methoxyindole, 6-hydroxyindole, 5-hydroxyindole, 7-hydroxyindole, 7-aminoindole, 5-aminoindole, 5,6-dihydroxyindole-2-carboxylic acid, 4-aminoindole, 1-methyl-5,6-dihydroxyindole, 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 4-hydroxy-5-methoxyindoline, 6-hydroxy-7-methoxyindoline, 6,7-dihydroxyindoline, 4,5-dihydroxyindoline, 5-methoxy-6-hydroxyindoline and their salts.
3. Process according to Claim 1 or 2, characterized in that the peroxidase is used at amounts of between 100 and 40 000 units per 100 g of components (1), (2) and (3) to be applied to the fibres.
4. Process according to any one of Claims 1 to 3, characterized in that the source of enzymatic hydrogen peroxide is composed of one or more natural substrate(s) in association with one (or more) oxidase enzymatic system(s) which catalyse(s) the oxidation of a substrate molecule by an oxygen molecule by transfer of a single oxygen atom.
5. Process according to Claim 4, characterized in that the substrate/enzyme system for oxidation by oxygen of the substrate by transfer of a single oxygen atom is chosen from the following systems:

   - glucose/glucose oxidase

   - galactose/galactose oxidase

   - pyranose/pyranose oxidase

   - L-sorbose/L-sorbose oxidase

   - ethanol/alcohol oxidase (1.1.3.13)

   - isopropanol/secondary alcohol oxidase (1.1.3.18)

   - pyruvic acid/pyruvate oxidase

   - oxalic acid/oxalate oxidase

   - aspartic acid/aspartate oxidase

   - glutamic acid/L-glutamate oxidase

   - uric acid/uricase

   - lactic acid/lactate oxidase

   or their mixtures.
6. Process according to Claim 4 or 5, characterized in that the oxidase enzymatic systems are used in amounts of between 100 and 20 000 oxidase catalytic units per 100 g of components (1), (2) and (3) to be applied to the keratinous fibres.
7. Process according to any one of Claims 1 to 6, characterized in that, in a first stage, a composition (A) comprising, in an aqueous medium appropriate for dyeing, at least the component (1) is applied to the keratinous fibres and then, in a second stage, a composition (B) comprising, in an aqueous medium appropriate for dyeing, at least the components (2) and (3) is applied to the keratinous fibres, the two stages optionally being separated by an intermediate rinsing, the pH of the compositions varying from 4.5 to 7.5.
8. Process according to Claim 7, characterized in that the leave-in time of the composition (A) is from 20 seconds to 20 minutes when the component (3) comprises hydrogen peroxide or from 1 minute to 1 hour when the component (3) comprises a source of enzymatic hydrogen peroxide and that the leave-in time for the composition (B) varies from 1 minute to 1 hour.
9. Process according to any one of Claims 1 to 6, characterized in that, in a first stage, a composition (C) comprising, in an aqueous medium appropriate for dyeing, at least the components (1) and (2) is applied to the fibres and, in a second stage, a composition (D) comprising, in an aqueous medium appropriate for dyeing, the component (3) is applied to the fibres, the pH of the compositions varying from 4.5 to 7.5.
10. Process according to Claim 9, characterized in that the leave-in time of the composition (C) varies from 20 seconds to 20 minutes and that the leave-in time of the composition (D) varies from 1 minute to 1 hour.
11. Process according to any one of Claims 1 to 6, characterized in that, in a first stage, a composition (E) comprising, in an aqueous medium appropriate for dyeing, at least the component (1) is applied to the fibres, in a second stage, a composition (F) comprising, in an aqueous medium appropriate for dyeing, the component (2) is applied to the fibres and then, in a third stage, a composition (G) comprising, in an aqueous medium appropriate for dyeing, the component (3) is applied to the fibres, the pH of the compositions varying from 4.5 to 7.5.
12. Process according to Claim 11, characterized in that the leave-in times of the compositions (E) and (F) vary from 20 seconds to 20 minutes and that the leave-in time of the composition (G) varies from 1 minute to 1 hour.
13. Process according to any one of Claims 1 to 12, characterized in that it comprises a final stage of rinsing and of drying.
14. Process according to any one of Claims 7 to 13, characterized in that the compound of formula (I) or (II) as defined in Claim 1 is used in proportions of between 0.2 and 5% by weight, with respect to the total weight of the composition (A), (C) or (E).
15. Process according to any one of Claims 7 to 14, characterized in that the hydrogen peroxide is used in proportions of between 0.03 and 10% by weight, with respect to the total weight of the composition (B), (D) or (G).
16. Process according to any one of Claims 4 to 15, characterized in that the natural substrate is present in proportions of between 1 and 25% by weight, with respect to the total weight of the component(s) (2) and/or (3).
17. Process according to any one of Claims 7 to 16, characterized in that the composition (A), (C) or (E) furthermore comprises an oxidation dye of the para and/or ortho type and/or couplers and/or a direct dye chosen from nitrobenzene derivatives, anthraquinones, naphthoquinones, benzoquinones and azo dyes.
18. Process according to any one of Claims 7 to 17, characterized in that the composition (A), (C) or (E) furthermore comprises a solvent chosen from lower alcohols, glycol ethers, glycol esters, glycols or lower esters.
19. Process according to any one of Claims 7 to 18, characterized in that at least one of the compositions (A) to (G) used comprises adjuvants chosen from anionic, cationic, nonionic or amphoteric surface-active agents or their mixtures, thickening agents, fragrances, sequestering agents, treatment agents, dispersing agents, conditioning agents, preservatives, agents for expanding keratinous fibres or their mixtures.